DE1276634C2 - PROCESS FOR PRODUCING MIXTURES OF SURFACE-ACTIVE COMPOUNDS - Google Patents

Description

benzthiazole, 2,5-dimercapto-l, 3,4-thiadiazole and many others.

The crude sulfonation mixtures, which are reacted with the aforementioned sultone reagents, can easily be prepared in a manner not claimed here by reacting olefins having 8 to 22 carbon atoms, the double bond of which is not in the position, with sulfur trioxide, the sulfur trioxide being in the form of mixtures with inert gases is used.

The olefins used as starting materials can be straight-chain or branched. They can also contain cycloaliphatic groups. The olefins do not have to be in pure form. They can be used in the form of meage, which is equivalent to the SO ₃ absorbed by the reaction mixture, assuming that for 1 mole of SO _? 1 equivalent of alkali is required. By adding a more or less large proportion of alkali during the neutralization, it is possible to adjust the content of the sultone reaction products in the end product in the desired manner. For the neutralization, depending on the intended use of the

ίο End product, use alkali hydroxides, in particular Sodium or potassium hydroxide, also alkali metal carbonates, ammonia, amines, such as triethanolamine and other bases. The bases can be used in the form of aqueous solutions. In special cases

technical mixtures are used, but they can also be solutions in suitable organic

Contain small amounts of paraffins or olefins. Use solvents, e.g. B. Solutions from

can. Sodium or potassium alcoholate in the concerned

For example, olefin mixtures with de-alcohol, especially methanol or ethanol, are suitable,

chain length, as in the case of the Fischer- The connections to be exposed are in the

Tropsch synthesis or, in the case of catalytic petroleum, is usually used in an amount sufficient for the implementation

crackung can be obtained. It can also be used such olefins by chlorination of Hydrocarbons and subsequent HCl elimination are won. Olefins obtained by isomerization of terminal olefins are also suitable will.

The gaseous sulfur trioxide used as the sulfonating agent is diluted with inert gases, with the sulfur trioxide concentration of the gas mixture with the sultones present in the mixture and others reactive sulfonic acid esters is sufficient. In general, the content of the reaction mixture is sultones and other reactive substances Sulfonic acid esters about 0.1 to 0.5 moles per mole of olefin.

It is advantageous to carry out the reaction at an elevated temperature with stirring. The co-use of organic solvents or thinners

1 to 20 percent by volume, preferably 2 to 10 volumetric agents, e.g. B. of lower aliphatic alcohol

percent, can be. Air and nitrogen are preferably considered as inert gases, but other gases, for example carbon dioxide or sulfur dioxide, are also suitable. It is expedient to proceed in such a way that the inert gas is passed through heated oleum or liquid, optionally heated sulfur trioxide, or SO _{3 is} evaporated in some other way in an inert gas stream. Sulfur obtained by burning sulfur or roasting sulfur-containing materials can also be reacted with air or oxygen.

len or ketones, is possible and in some cases, which are very viscous products are recommended. The presence of water interferes with the generally not.

In some cases, the bases used for neutralization can also be used at the same time as those to be exposed Compounds are added. For example, one can use the crude sulfonation products with a mixture of sodium hydroxide solution and trialkylamine

catalytically oxidize thin sulfur dioxide to sulfur trioxide. Such mixtures can be used directly for sulfonation can be used. Small amounts of sulfur dioxide do not interfere.

The mixtures of surface-active compounds produced with the aid of the process according to the invention exhibit different properties depending on the compounds used for exposure

The sulfonation can be carried out by known methods. If an amine is used, e.g. If, for example, dodecyldimethyl are carried out, in the simplest case by monoamine, the reaction products have a gas stream containing sulfur trioxide in advance
into the olefin to be sulfonated. One can use the sulfonic

tion continuously or discontinuously at the same time Di Slfi id

Excellent foam-stabilizing effect, so that, with the aid of the reaction mixtures, detergents and cleaning agents, for example, with particularly good foam or countercurrent flow can be carried out. The sulfonic: ng will make 50 gain stability. Thus, the foam stability was performed, for example an aqueous solution of and + 6O ⁰ C, generally at temperatures between about -10. One works appropriately
in a temperature range of about 10 to 45 "C.

16 parts by weight (pbw) tetrapropylene benzene sulfonate, 1.2 pbw p-tol'iolsulfonate, 37 pbw sodium pyrophosphate, 5 parts by weight of water glass, 12.7 parts by weight of sodium sulphate and, expediently, at least 1 mole of sulfur trioxide per 55 parts by weight of carboxymethyl cellulose, which is about one mole To use olefin. Preferably, 1.1 to average basic detergent compositions are g ent-1.3 Moles of sulfur trioxide applied. The application speaks, once for itself, once with an addition

p
To achieve a good level of sulfomer it is

, g g

a larger excess of up to about 1.7 moles of SO ₃ per mole of olefin is possible.

of the coconut fatty acid known as a foam stabilizer! iionoäthanolamids and on the other hand with the after

The crude reaction product can be directly obtained with 60 products obtained in Example 1 of the present invention suitable compounds are implemented. The duct measured. The investigation was carried out after

in

In addition to sultones, sulfonation products generally contain a more or less large proportion of acidic reaction products. It has therefore usual laboratory methods in a Miele Rührfiügelmaschine M 75 with 15-minute mechanics at 95 ⁰ C at a use concentration van 3 g

In many cases it has proven advantageous to use the crude sulfo 65 dry matter per liter and a water hardness of

nation producf. neutralize before adding the compounds. For the neutralization are here mostly about 60 to 95%, preferably 80 to 90%, of the alkali

16 ° dH. The liquor was loaded with normally soiled household linen. The foam height formed was immediately after the expiry of the

12th

Machine and after 1, 3, 5 and 10 minutes. The values given in the following table are mean values from several readings and on Rounded up to 0.5 cm. As can be seen from the table, with a suitable product is already used with an addition of only 0.7 percent by weight of substance achieves a foam height that with a conventional Stabilizer is only achieved at an amount of 3 percent by weight.

Tem Time Foam height (cm) concentrate pera-
ri »r concentrate concentrate + 0.7% does alone + 3% coconut example 1 fatty acid mono- ( ⁰ Q (Wed ethanolamide grooves) 11.0 0 7.0 10.5 10.5 1 6.0 10.0 10 80 3 4.5 9.5 9 5 2.5 8.5 8th 10 0.5 6.5 10.5 0 6.0 10.0 9.0 1 5.0 9.0 7.5 60 ■ 3 3.0 8.5 6th 5 1.0 7.0 4.5 10 0.0 5.5 7.5 0 5.0 8.0 6.5 1 4.5 7.5 4.0 40 3 1.5 4.5 2.5 5 1.5 3.0 1.5 10 1.5 2.0

In other cases, for example when using compounds containing sulfur or sulfur and Containing nitrogen, such as mercaptobenzothiazole or thiourea, give the sultone reaction products the mixtures have a good anti-corrosive effect. The implementation with tertiary amines often leads also to compounds with good disinfectant or bacteriostatic effectiveness.

example 1

In a 3-necked flask of 2 1 content that was provided with a thermometer, to the bottom of the piston reaching gas inlet tube, a gas outlet and an intensive stirrer, 270 g (1.2 mol) of a straight chain C _ie olefin mixture with double bonds statistically distributed over the carbon chain and a content of less than 10% «-olefin. The olefin mixture was sulfonated with vigorous stirring by blowing in an SO ₃ / air mixture which contained about 3 percent by volume of SO _3. In the course of one hour, 112 g of SO ₃ (1.4 mol) were passed in. The temperature of the reaction mixture was kept at 15 to 25 ° C. by external cooling. After the sulfonation had ended, a solution of 32 g of NaOH (0.8 mol) in 200 ml of water was added in portions to the low-viscosity reaction product, while stirring and cooling. Then, 100 ml of a 40% aqueous solution of trimethylamine was added and the reaction mixture heated for 1 hour in ¹ I ₂ an autoclave of capacity 21 to 12O ⁰ C. The solution was then neutralized by adding a small amount of dilute sulfuric acid and using a Krause spray dryer at 90 to 100 ^° C.

634 I /

I 6

converted into a dry powder. 407 g of a yellow-colored substance were obtained which were dissolved in water was readily soluble and gave strongly foaming solutions. The reaction product had the following key figures:

Acid number 0

Saponification number 0

Iodine number 29.7

OH number 29.2

N content 1.08%

The substance did not contain free trimethylamine or trimethylammonium sulfonate. the end the nitrogen value found results in a content of 28.4% of a trimethylammonium sulfo-

X5 betains in the reaction product.

In another approach of the same type, the product was previously sprayed with sodium hypochlorite bleached. For this purpose, the neutralized solution was 4% (based on the sulfonation product)

ao NaClO heated for 2 hours under gentle stirring at 50 to 60 ⁰ C. In this way, a practically colorless spray powder was obtained.

Example 2

In the apparatus described in Example 1, 236 g (1.2 mol) of a straight-chain C ^ -olefin mixture with double bonds randomly distributed over the carbon chain and a content of less than 10% α-olefin were sulfonated. To this end, 115 g of sulfur trioxide (1.44 mol) in the form of an SO ₃ -air mixture, which contained about 3 percent by volume of SO ₃ , were introduced over the course of one hour with vigorous stirring. The temperature was increased by external cooling

door of the reaction mixture between 10 and 20 ⁰ C kept. After the sulfonation had ended, a solution of 34 g of NaOH (0.85 mol) in 300 ml of water was added in portions to the low-viscosity reaction product, while stirring and cooling. The product obtained was then added in portions with stirring at about 40 ° C. to a solution of 0.6 mol of sodium Ν, Ν-diethyldithiocarbamic acid. This latter solution was prepared by reacting 45.5 g of carbon disulfide, 43.5 g of diethylamine and 300 ml of 8% strength sodium hydroxide solution. After the addition had ended, the reaction mixture was refluxed with stirring for 3 hours. The solution was then neutralized with dilute sulfuric acid and ^{sprayed at 90 to 100 °} C. in a Krause atomization dryer. 452 g of a solid yellow substance were obtained which was readily soluble in water and gave strongly foaming solutions.

Example 3

In the same apparatus as in Example 1, 332 g (1.32 mol) of a straight-chain C ₁₈ olefin mixture with double bonds randomly distributed over the carbon chain and a content of less than 10% of α-olefins were sulfonated. For this purpose, 126 g of SO ₃ (1.58 mol) in the form of an SO ₃ -air mixture containing about 3 percent by volume of sulfur trioxide were blown in over the course of 1/2 hour with vigorous stirring. The temperature of the reaction mixture between 20 and 3O ⁰ C was maintained by external cooling. After the sulfonation had ended, the low-viscosity reaction product was mixed in portions with a solution of 36.4 c with stirring and cooling

7 8

(0.91 mol) in 200 ml of water were added. The obtained ^{heated to 120 0} C and the obtained solution to dryness

Mixture was evaporated in portions with stirring at about. The residue from evaporation was 568 g

40 ⁰ C to a solution of 131 g of 2,4,6-trichlorophenol of a solid, yellow-brown substance obtained, the fol-

(0.67 mol) in 330 ml of 8% sodium hydroxide solution. had the following key figures:

The strongly foaming reaction mixture was 5

then reflux for 5 hours with stirring at Tm in 7

cooks. Then the solution was diluted with oh 7 hl ο ι

Sulfuric acid and neutralized with the help of a Krause- Γ η u ι ,, \ _{o /}

Spray dryer at 100 ⁰ C in a dry [,? Nr ϊ'ύ οίο /

Powder transferred. 608 g of a yellow-colored iNa ₂ :> u ₄ -uenait ν, α ^

th substance obtained that was readily soluble in water. · Ι .-

and gave high foaming solutions. b e ι s ρ ι e 1.)

In a further approach of the same type, the apparatus described in Example 1 was

the sulphonation deneutralized with sodium hydroxide solution 236 g (1.2 mol) of a straight-chain C ₁₄ -OIeBn-

product with the sodium 2,4,6-trichlorophenolate 15 mixture with statistical information about the carbon chain

by heating for 2 hours at 130 ° C in an autoclave to the distributed double bonds and a content of

Implementation brought. In this case, a product was sulfonated with less than 10% olefin. For this were

keep, which with the above-described 115 g of sulfur trioxide (1.44 mol) in the form of an SO ₄ -

was practically identical. Air mixture containing about 3 percent by volume SO ₃

ao held, stirring vigorously over the course of an hour

Example 4 initiated. The temperature of the reaction mixture from 10 to 20 ⁰ C by external cooling was

The apparatus described in Example 1 was used. After the sulfonation had ended, the 332 g (1.32 mol) of a straight-chain Cij -olefin thin liquid reaction product was obtained with cooling with a mixture with a solution of 0.95 mol of sodium ethylate (divided double bonds and a content of 66%, depending on the carbon chain). Sodium ethylate, based on less than 10% of α-olefin, was sulfonated. For this purpose, SO ₃ ) in 400 ml of absolute ethanol and 126 g (1.58 mol) of sulfur trioxide in the form of SO ₃ - then with a solution of 41 g of sodium acetate in air -Mixture containing about 3 percent by volume of SO ₃ (0.5 mol) in 400 ml of methanol. Then held, in the course of I ¹ J ₂ hours with vigorous Ruh- 30 3 Stunren was introduced into an alkali-resistant 2-1 autoclave. The tempera- was the heated to 140 ⁰ C and the resulting solution then evaporated temperature of the reaction mixture from 20 to 30 ⁰ C by external cooling to dryness. These were held as. After the sulfonation had ended, the vapor residue was 434 g of a yellow, solid substance, a thin-bodied reaction product which weighed 458 g and had the following characteristics:
while cooling with a solution of 0.91 mol of sodium 35

ethylate (corresponding to 58% sodium ethylate, based on acid number 0

on absorbed SO ₃ ) in 300 ml of absolute ethanol, saponification number 0

added and then with a solution of 102 g of iodine number 29.6

(0.68 mol) of sodium iodide in 500 ml of ethanol were added. OH number 6.5

Then in a 2-1 autoclave for 3 hours 40 Na ₂ SO ₄ content 9.9%

Claims (3)

* · .., claims: 1. Process for the preparation of mixtures of surface-active compounds, according to the main patent 12 18434, t characterized by the fact that in a manner known per se Place of sulphonation mixtures obtained by sulphonation of -olefins with 8 to 22 carbon atoms with 1 to 1.7 moles of sulfur trioxide have been obtained, sulfonation mixtures obtained by Sulphonation of olefins of the general formula R ₁ -CH = CH-R, where R ₁ and R, are identical or different alkyl or cycloalkyl radicals with a total of 6 to 20 carbon atoms, have been obtained with 1 to 1.7 mol of sulfur trioxide, neutralized and with halides, amines, alcoholates, phenolates, carboxylic acid salts and salts of SH -Groups-containing compounds. 2. The method according to claim 1, characterized in that one neutralization and others Implementation at the same time. 3. The method according to claim 1 and 2, characterized in that the compounds to be converted added in an amount necessary to react with those present in the mixture Sultones and other sulfonic acid esters are sufficient. The invention relates to a development of the main patent 12 18 434, which describes a method for »The subject matter of mixtures of surface-active compounds, which thereby kennleichnet is that one in a known manner sulfonation mixtures by sulfonation of «-Olefins having 8 to 22 carbon atoms with 1 to 1.7 moles of sulfur trioxide per mole of olefin have been neutralized and treated with halides, amines, alcoholates, phenolates, carboxylic acids Sa! - ien and salts of compounds containing SH groups implements. In this way, not only those present in the mixture are reacted Sultones formed by sulfur trioxide in the olefin, but also other sultones formed during sulfonation Sulfonic acid ester implemented. In many cases, this gives rise to compounds which are part of the mixture of surface-active substances Particularly valuable properties conferred on compounds. It has now been found that high-quality mixtures of surface-active compounds can also be obtained comes when in a known manner in place of sulfonation mixtures by sulfonation of «-olefins with 8 to 22 carbon atoms with 1 to 1.7 mol of sulfur trioxide have been obtained, Sulphonation mixtures obtained by sulphonation of Olefins of the general formula R ₁ -CH = CH-R ₂ where R ₁ and R, identical or different aliryl or cycloalkyl radicals with a total of 6 to 20 carbon atoms, have been obtained with 1 to 1.7 mol of sulfur trioxide, neutralized and with halides, amines, alcoholates, phenolates, carboxylic acid salts and sateen from SK -Gruppcn-containing compounds. It is known that sultones react with a large number of alkylatable compounds, among others others with those that contain a reactive hydrogen atom. These compounds are preferred in the form of their salts, in particular their alkali metal or ammonium salts, or in the presence acid-binding agents implemented with sultones. Suitable substances are e.g. B. alcohols, phenols, hydroperoxides, Carboxylic acids, primary or secondary! 5 amines, imines, carboxylic acid or sulfonic acid amides, Carboxylic acid imides or sulfonic acid imides, oximes and compounds containing SH groups, such as mercaptans, Thiol acids, dithio acids, xanthogenic acids, Dithiocarbamic acids, trithiocarbonic acid and sulfinao acids. These compounds can be aliphatic, They can also contain one or more of the aforementioned have reactive groups. Also salts of the hydrohalic acids, the as hydrothodanic acid, the thiosulphuric acid and of the hydrogen sulfide can be reacted with sultones. Some compounds that contain active hydrogen can also be converted with sultones, without that the simultaneous presence of acid-binding agents would be required or without the relevant Substances should be present in salt form. Such compounds are e.g. B. the thiourea and its am Nitrogen-substituted derivatives, also sulfonic acid amides and hydrohalic acids. Furthermore, such compounds can also be made to react with sultones, their reactivity not through an active hydrogen atom, but through one that can be converted into a higher bond level Atom is conditional, e.g. B. tertiary amines, thioethers and tertiary phosphines. Because the reaction of the sultones present in the mixture in the presence of large amounts of foreign substances as well as in many cases also carried out in the presence of water, are in the Process according to the invention, the sultones are preferably implemented with substances that are quick and energetic react. Such substances are z. B. amines, especially tertiary amines, such as trimethylamine or triethylamine, or those tertiary amines which have a longer chain contain an aliphatic radical in the molecule, such as octyldimethylamine or dodecyldimethylamine. Even cycloaliphatic, aromatic and heterocyclic amines are suitable, such as cyclohexylamine, dicyclohexylamine, Dimethylcyclohexylamine, aniline, dimethylaniline, pyridine, alkylpyridines, piperidine and many other. Furthermore, alcoholates or phenates are suitable, for. B. sodium methylate, sodium ethylate, potassium octylate, Sodium dodecylate, sodium phenolate, as well as salts of various substituted phenols, such as sodium trichlorophenolate, Potassium nonylphenolate and the like In particular, the sultones react with compounds containing SH groups. Suitable Substances are, for example, alkali or ammonium salts of mercaptans or thiophenols, N-substituted Dithiocarbamic acids, such as Ν, Ν-diethyldithiocarbamic acid, Trithiocarbonic acid, mercapto-